Copper-containing disazo dyestuffs



2,815,337 COPPER-CONTAINING DISAZO DYESTUFFS Fritz Kehrer, Basel, and Walter Wehrli, Riehen, near Basel, Switzerland, assignors, by mesne assignments, to Saul & Co., Newark, N. J., as nominee of Fidelity UnionTrust Company, executive trustee under Sandoz Trust No Drawing. Application March 7, 1955, Serial No. 492,745

Claims, priority, application Switzerland Mar-ch17, 1954 6 Claims. (Cl. 260-148) It 'has been found that very valuable copper complex disazo dyestuffs are obtained when the symmetrical urea of 2-amino-5-hydroxynaphthalene-7-sulfonic acid is coupled in either .order with a diazotizedaminobenzene of the general formula INHB S Or -W wherein B stands for hydrogen or methyl, and W stands for adower; aliphatic or carbocyclic hydrocarbon radical, and with thediazo compound of an amine of the general formula land the alkyl and arylsulfonyl groups merit special: mention.

The dyestuffs areobtained by combining the monoazo compound formed from 1 molof a diazotiZed-aminobenzene (I) and 1 mol of the symmetrical urea of 2-amino-5- "hydroxynaphthalenefl-sulfonic acid with 1 mol of a diazotizedaminobenzene (II), or alternatively by prepargiug themonoazo compound from 1 mol of a diazotized -aminobenzene- (II) and 1' molofthe symmetrical ureaef- 2-amino:SehydrQXynaphthaIene-7-sulfonic acid and coupling it with 1 mol of a diazotizedvaminobe'nzene '(I). The resulting disazo dyestuifs are converted into-the copper complex compounds in substance or on the :fiber; Coupling is carried out preferably in a weakly alkaline medium. -In cases where the uncoppered dyestutf con tains a methoxy groupin. ortho-position to the azo bridges,

.themethodlof. converting employed must produce simultaneous splitting of the methoxy group.

iT'he new disazo dyestuffs in their unmetalli-zed form correspond tolthe general formula rye Patent" Example 1 18.8 parts of 1-amino-2-hydroxybenzene-S-sulfonic acid amide are stirred'into 800 parts of water and 23 parts of concentrated hydrochloric acid. When the suspension has cooled-toO-S", 6.9 parts ofsodium nitrite are added. The diazo suspension 'thusfformed is run into a'solution -of-'54;8 parts *o'f the symmetrical urea of 2-amino 5-hy- -droxynaphthalene=7-sodium sulfonate, 16.8 parts'of -sodium bicarbonate and 1300 parts of water. On formation of the monoazo compound, 26.5 parts of anhydrous gsodium carbonate-aare added to thereaction product,-folrlowed byi thediazo suspension of 18.7 parts-ofl-amino- ,Z-hydroxy-5+methylsulfonylbenzene. The fine disperse 1disazodyestuif thus obtained is broughtiinto solution, at -85 by the additionuof 1600 parts of water and 7.4 parts of concentrated caustic soda to the couplingmass, precipitated by means of sodium chloride, filtered off and ,dried. ,Itcorresponds to the formula SIOTCH3 For -converting into the copper complex, the separated disaz'ofdyestuff is dissolved at 80 85 -in 4800 parts of water and 35$5 parts of 25% ammonia. To this solution dsaddedaflthe same temperature 54.4 parts of crystallized :sodiurn acetate'aniin the course of 30 minutesja solution of 50 parts of crystallized copper sulfate in-SOO-parts of water. i The coppering mass is agitated for a fu rther 60 minutes atrthe same temperature, after-which time the separated copper complex disazo dyestuif is filtered on and .vacuum dried at It corresponds to'the formula I SOz-CH;

and possesseshigh a'ffinity for cotton and 'fibers of regener'ated cellulose which'it dyes in"'brigh't"Bordeaux shades 70 l-amino 2-methoxybenzene-5 sulfonic acid amide; .or "1- amino-2-methoxy-S-methylSulfonylbeniene and l-amin'o- Z-hydroxybenzene-S-sulfonic acid amide; and" subjecting The disazo dyestuff obtained from20j2pa rts of diazotized 1-amino-2-methoxybenZene SEsuIfonic. 'acidlamide,

18.7 parts of diazotized l-amino-Z-hydroxy 5-methylsu1- fonyl-benzene and 54.8 partsbfthe'symmetriczil urea of 2-amino-S-hydroxynaphthalene-7-sodium sulfonate is dispersed in the form of an aqueous paste for 1 hour in a solution of 180 parts of sodium chloride 'in 1400 parts of water at 80-85". To this suspension is added at the same temperature over a period of 30 minutes a solution of 50 parts of crystallized copper sulfate, 500 parts of water and 64 parts of 25% ammonia; the coppering mass is then heated for 12-16 hours under reflux. After this time demethylating and coppering are completed. The copper-containing disazo dyestuff thus formed possesses the same properties as that described in the second paragraph of this example.

Example 2 When the 18.8 parts of l-amino-2-hydroxybenzene-5- sulfonic acid amide of the foregoing example are replaced by 13.7 parts of l-amino-2-carboxylic acid, subsequent converting results in a copper-containing disazo dyestufi corresponding to the formula This dyestuif dyes cotton and fibers of regenerated cellulose in bright yellowish Bordeaux shades of very good fastness to light.

In the preceding example a ratio of 1:1 is chosen for the two diazo components. When this ratio is varied equally valuable products are obtained which yield Bordeaux dyeings correspondingly yellower or bluer in hue than those obtained with the dyestufl described in Example 2.

The following table lists other disazo dyestuffs obtained by coupling 1 mol of the symmetrical urea of the Z-amino-S-hydroxynaphthalene-7-sulfonic acid with 1 mol each of the diazo components (I) and (II). The dyestuffs are characterized by the amines from which the two diazo components are derived and by the shades of the. dyeings of the copper-containing dyestuffs on cotton.

- V 4 dyeing the material is left in the bath for 15-20 minutes to cool to 50, then withdrawn and rinsed and dried.

This method is also employed for dyeing fibers of regenerated cellulose. It is applicable with all the dyestuffs described in the foregoing examples.

In many cases aftertreatment of the dyeing with copper salts, especially when applied in conjunction with cationactive compounds, leads to improved fastness properties.

The formulae of the metal-free disazo dyestuffs of representative members of this invention are as follows:

Example 3 0H OH OH OH HO; NH-GO- BOgH Or-CH: r I

Example 4 OH OH OH OH HO; NH-CO- BOaH SOs-CH: 801K Example 6 OH OH OH OH N=N N=N HO; NH-CO-NH 80 E SOs-CH; BO NH-C I Having thus disclosed the invention. what is claimed is: l. A copper complex compound of a disazo dyestuff which corresponds to the formula wherein:

BOaH

Example Shade of the dyeing of No. Dtazo compound (I) Dlazo compound (II) the copper-containlngdyestufloncotton 3 1-amino-2-hydroxy-5-methylsnlfonylbenzene 1-amino-2-hydroxy-S-methylsulfonylbenzene Bright Bordeaux.

4 do 1-amino-2-hydroxybenzene-5-sultonic acid... Do.

5 1'amino-2-methoxybenzene-fi-sulfonic acid-. Do.

a l-amtno-2-hydroxybenzene-fi-sullonic acid methylamide.. Do.

7 1-amino-2-hydroxybenzene-fi-sulfonic acid phenylamide. Do.

a do 1-amino-2-hydroxy-3-chl0r0benzene-5-sulf0nlc acid. D0. l-amlno-2-hydr0xy-5-phenylsulfonylbenzene. l-amino-2-methoxybenzene-S-sulfonic acid Do. l-amino-Z-rnethoxy-fi-phenylsulfonylbenzene D0.

1-amino-2-hydroxy-5-ethylsulfonylbenzene. l-amino-2 hydroxybenzene-Ii-sultonlc acid Do. 1-amino-Z-hydroxy-5-methy1sultonylbenzen 1-am1no-2-carboxybenzene-4 sulfonic acid amide Do.

Example 13 10 parts of cotton are wet out in a dyebath at 50 containing 300 parts of soft water. 0.1 parts of the dyestufi of Example 1 in concentrated aqueous solution are added to the bath, which is then heated to the boil in 30 minutes and maintained at the boil for 15 minutes. During the dyeing process 3-4 parts of sodium sulfate in concentrated aqueous solution are added. On completion of 2 A copper complex compound of a disazo dyestufl which corresponds to the formula (I)H OH OH OH =N N=N- HOzS- NH-CO-NH 50311 802-0113 SO NH 3. A copper complex compound of a disazo dyestufi which corresponds to the formula 0H OH OH OH HO: NH-C O-NH SOsH Soy-CH; SOr-CH;

4. A copper complex compound of a disazo dyestufi which corresponds to the formula Og-CH;

5. A copper complex compound of a disazo dyestufi which corresponds to the formula OH OH OH SOr-CH; 503K 6. A copper complex compound of a disazo dyestufi which corresponds to the formula 0H 0H 0H N N=N HOrS NH-c o-NH S0311 sol-0H: i m-0H:

References Cited in the file of this patent UNITED STATES PATENTS 2,128,255 Krzikalla et a1. Aug. 30, 1938 2,538,568 Kaiser et a1 Jan. 16, 1951 2,633,462 Kehrer et a1. Mar. 31, 1953 

1. A COPPER COMPLEX COMPOUND A DISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 